US6838409B1 - Catalyst for olefin/styrene copolymerization, and process for producing olefin/styrene copolymer - Google Patents
Catalyst for olefin/styrene copolymerization, and process for producing olefin/styrene copolymer Download PDFInfo
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- US6838409B1 US6838409B1 US09/914,254 US91425401A US6838409B1 US 6838409 B1 US6838409 B1 US 6838409B1 US 91425401 A US91425401 A US 91425401A US 6838409 B1 US6838409 B1 US 6838409B1
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- 0 *c1*([RaH])c(*)c(*)c1*.*c1c(*)c(*)c2c(*)c(*)c(*)c2c1*.*c1c(*)c(*)c2c(c1*)c(*)c(*)c1c(*)c(*)c(*)c12.*c1c(*)c(*)c2c(c1*)c(*)c1c(*)c(*)c(*)c(*)c12.*c1c(*)c(*)c2c3c(c(*)c2c1*)*([RaH])C([RaH])*3[RaH].*c1c(*)c2c(c1*)*([RaH])C([RaH])*2[RaH].*c1c2c(c3c1*([RaH])C([RaH])*3[RaH])*([RaH])C([RaH])*2[RaH] Chemical compound *c1*([RaH])c(*)c(*)c1*.*c1c(*)c(*)c2c(*)c(*)c(*)c2c1*.*c1c(*)c(*)c2c(c1*)c(*)c(*)c1c(*)c(*)c(*)c12.*c1c(*)c(*)c2c(c1*)c(*)c1c(*)c(*)c(*)c(*)c12.*c1c(*)c(*)c2c3c(c(*)c2c1*)*([RaH])C([RaH])*3[RaH].*c1c(*)c2c(c1*)*([RaH])C([RaH])*2[RaH].*c1c2c(c3c1*([RaH])C([RaH])*3[RaH])*([RaH])C([RaH])*2[RaH] 0.000 description 11
- NPGYNOJKOUFHNO-FOBLQCDGSA-N CC(C)c1cccc(C(C)C)c1N1=C2C(=N(c3c(C(C)C)cccc3C(C)C)[Ni]1(C)C)c1cccc3cccc2c13.CC(C)c1cccc(C(C)C)c1N1=CC=N(c2c(C(C)C)cccc2C(C)C)[Ni]1(C)C.CC1=N(c2c(C(C)C)cccc2C(C)C)[Ni](C)(C)N(c2c(C(C)C)cccc2C(C)C)=C1C.[H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=CC=N1c1c(C(C)C)cccc1C(C)C Chemical compound CC(C)c1cccc(C(C)C)c1N1=C2C(=N(c3c(C(C)C)cccc3C(C)C)[Ni]1(C)C)c1cccc3cccc2c13.CC(C)c1cccc(C(C)C)c1N1=CC=N(c2c(C(C)C)cccc2C(C)C)[Ni]1(C)C.CC1=N(c2c(C(C)C)cccc2C(C)C)[Ni](C)(C)N(c2c(C(C)C)cccc2C(C)C)=C1C.[H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=CC=N1c1c(C(C)C)cccc1C(C)C NPGYNOJKOUFHNO-FOBLQCDGSA-N 0.000 description 1
- JDRFSLJNWMRCNZ-YGMULEPDSA-H CC(C)c1cccc(C(C)C)c1N1=CC=N(c2c(C(C)C)cccc2C(C)C)[Ni]1(Br)Br.CCc1cccc(C(C)C)c1N1=C(C)C(C)=N(c2c(CC)cccc2C(C)C)[Ni]1(Br)Br.CCc1cccc(C(C)C)c1N1=C2C(=N(c3c(CC)cccc3C(C)C)[Ni]1(Br)Br)c1cccc3cccc2c13 Chemical compound CC(C)c1cccc(C(C)C)c1N1=CC=N(c2c(C(C)C)cccc2C(C)C)[Ni]1(Br)Br.CCc1cccc(C(C)C)c1N1=C(C)C(C)=N(c2c(CC)cccc2C(C)C)[Ni]1(Br)Br.CCc1cccc(C(C)C)c1N1=C2C(=N(c3c(CC)cccc3C(C)C)[Ni]1(Br)Br)c1cccc3cccc2c13 JDRFSLJNWMRCNZ-YGMULEPDSA-H 0.000 description 1
- OBSHTNANSJJHKO-PAUXOATKSA-N [H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=C(C)C(C)=N1c1c(C(C)C)cccc1C(C)C.[H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=C2C(=N1c1c(C(C)C)cccc1C(C)C)c1cccc3cccc2c13.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=C(C)C(C)=N1c1c(C(C)C)cccc1C(C)C.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=C2C(=N1c1c(C(C)C)cccc1C(C)C)c1cccc3cccc2c13.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=CC=N1c1c(C(C)C)cccc1C(C)C Chemical compound [H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=C(C)C(C)=N1c1c(C(C)C)cccc1C(C)C.[H][Ni]1(C)N(c2c(C(C)C)cccc2C(C)C)=C2C(=N1c1c(C(C)C)cccc1C(C)C)c1cccc3cccc2c13.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=C(C)C(C)=N1c1c(C(C)C)cccc1C(C)C.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=C2C(=N1c1c(C(C)C)cccc1C(C)C)c1cccc3cccc2c13.[H][Ni]1([H])N(c2c(C(C)C)cccc2C(C)C)=CC=N1c1c(C(C)C)cccc1C(C)C OBSHTNANSJJHKO-PAUXOATKSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Definitions
- the present invention relates to catalysts for copolymerization of olefins and styrenes, and to methods for producing olefin-styrene copolymers. Precisely, it relates to catalysts for olefin-styrene copolymerization comprising, as one component, a specific compound, and to inexpensive and efficient methods for producing olefin-styrene copolymers with the catalysts.
- metallocene catalysts have been developed and used for olefinic polymer production, which comprise, as the catalyst component, a transition metal compound having a n-ligand bonded to the center metal element via a group.
- the catalysts of that type require a large amount of promoters such as aluminoxanes and the like. Therefore, they are problematic in that the total catalyst costs are inevitably high, and, in addition, the catalyst residue resulting from the promoter used often remains in the polymers produced thereby unfavorably coloring the polymers.
- the present invention is to provide catalysts for olefin-styrene copolymerization capable of efficiently and inexpensively producing olefin-styrene copolymers, and to provide methods for producing olefin-styrene copolymers.
- the present inventors have assiduously studied so as to attain the object as above, and, as a result, have found that copolymerization catalysts containing, as one component, a specific compound have improved copolymerization activity and therefore the amount of the promoters such as oxygen-containing compounds and others to be used with them can be reduced. On the basis of this finding, we have completed the present invention.
- the invention is to provide a catalyst for copolymerization of olefins and styrenes and a method for producing olefin-styrene copolymers, which are as follows:
- the catalyst of the invention for copolymerization of olefins and styrenes comprises (A) a transition metal compound, (B) an oxygen-containing compound and/or a compound capable of reacting with a transition metal compound to form an ionic complex, and (C) a compound of formula (1) which will be described in detail hereinunder, and optionally (D) an alkylating agent.
- A a transition metal compound
- B an oxygen-containing compound and/or a compound capable of reacting with a transition metal compound to form an ionic complex
- C a compound of formula (1) which will be described in detail hereinunder
- D an alkylating agent
- transition metal compounds are usable as the component (A) in the invention, but preferred are transition metal compounds of Groups 4 to 6 of the Periodic Table, or transition metal compounds of Groups 8 to 10 thereof.
- transition metal compounds of Groups 4 to 6 of the Periodic Table preferred are those of the following general formulae (2) to (5).
- transition metal compounds of Groups 8 to 10 of the Periodic Table preferred are those of the following general formula (6).
- Q 1 and Q 2 in formulae (2) and (3) include (1) an alkylene group having from 1 to 4 carbon atoms, or a cycloalkylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, a cyclohexylene group, etc.; (2) a silylene group, or an oligosilylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a silylene group, a dimethylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, a disilylene group, a tetramethyldisilylene group, etc.; and (3) a hydrocarbon group (e.g., a lower alkyl group, a phenyl group, or
- the hydrocarbon group preferably has from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms.
- the hydrocarbon group may be a monovalent one that bonds to the cyclopentadienyl group of a conjugated, 5-membered cyclic group. Two of plural hydrocarbon groups, if any, may be bonded to each other to form a cyclic structure along with a part of the cyclopentadienyl group.
- Specific examples of those conjugated, 5-membered cyclic ligands are substituted or unsubstituted cyclopentadienyl groups, indenyl groups and fluorenyl groups.
- the halogen atom includes chlorine, bromine, iodine and fluorine atoms.
- the alkoxy group preferably has from 1 to 12 carbon atoms.
- the silicon-containing hydrocarbon group includes, for example, groups of —Si (R 12 ) (R 13 ) (R 14 ), in which R 12 , R 13 and R 14 each represent a hydrocarbon group having from 1 to 24 carbon atoms.
- the nitrogen-containing hydrocarbon group and the boron-containing hydrocarbon group for example, mentioned are groups of —P(R 15 ) (R 16 ), —N(R 15 ) (R 16 ), and —B(R 15 ) (R 16 ), respectively, in which R 15 and R 16 each represent a hydrocarbon group having from 1 to 18 carbon atoms.
- R 8 's, R 9 's and R 10 's may be the same or different ones, respectively.
- the conjugated, 5-membered cyclic ligands (C 5 H 5-a-b R 8 b ) and (C 5 H 5-a-c R 9 c ) may be the same or different ones.
- M 1 represents a transition metal element of Groups 4 to 6 of the Periodic Table, including, for example, titanium, zirconium, hafnium, niobium, molybdenum, tungsten, etc. Of those, preferred are titanium, zirconium and hafnium, and more preferred is zirconium.
- Z 1 represents a covalent-bonding ligand, including, for example, oxygen (—O—), sulfur (—S—), an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, a thioalkoxy group having from 1 to 20, preferably from 1 to 12 carbon atoms, a nitrogen-containing hydrocarbon group having from 1 to 40, preferably from 1 to 18 carbon atoms, and a phosphorus-containing hydrocarbon group having from 1 to 40, preferably from 1 to 18 carbon atoms.
- X 1 and Y 1 each represent a covalent-bonding ligand, including, for example, a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20, preferably from 1 to 10 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a diphenylphosphine group, etc.), a silicon-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a trimethylsilyl group, etc.), and a boron compound residue having a hydrocarbon group with from 1 to 20, preferably from 1 to 12 carbon atoms or having halogens (e.g., B(C 6 H 5 ) 4 , BF 4 ). Of those, preferred are halogen atoms and hydrocarbon groups.
- X 1 and Y 1
- M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table, such as that mentioned above; and X 1 and Y 1 have the same meanings as above. The meanings of X 1 and Y 1 shall apply to W 1 .
- W 1 is a covalent-bonding ligand, including, for example, a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20, preferably from 1 to 10 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a diphenylphosphine group, etc.), a silicon-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a trimethylsilyl group, etc.), and a boron compound residue having a hydrocarbon group with from 1 to 20, preferably from 1 to 12 carbon atoms or having halogens (e.g., B(C 6 H 5 ) 4 , BF 4 ). Of those, preferred are halogen atoms and hydrocarbon groups.
- X 1 , Y 1 and W 1 may be
- M 1 represents a transition metal of Groups 4 to 6 of the Periodic Table, such as that mentioned above; and X 1 , Y 1 and W 1 have the same meanings as above. The meanings of X 1 , Y 1 and W 1 shall apply to U 1 .
- U 1 is a covalent-bonding ligand, including, for example, a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20, preferably from 1 to 10 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a diphenylphosphine group, etc.), a silicon-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a trimethylsilyl group, etc.), and a boron compound residue having a hydrocarbon group with from 1 to 20, preferably from 1 to 12 carbon atoms or having halogens (e.g., B(C 6 H 5 ) 4 , BF 4 ). Of those, preferred are halogen atoms and hydrocarbon groups.
- transition metal compounds of formulae (2) and (3) mentioned are the following compounds.
- titanium may be replaced with zirconium, and such zirconium compounds are also referred to herein to the same effect.
- Transition metal compounds not having a crosslinkable bonding group but having two conjugated, 5-membered cyclic ligands such as 0.17 bis(cyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl)titanium dichloride, bis(dimethylcyclopentadienyl)titanium dichloride, bis(trimethylcyclopentadienyl)titanium dichloride, bis(tetramethylcyclopentadienyl)titanium dichloride, bis(pentamethylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)titanium dichloride, bis(indenyl)titanium dichloride, bis(fluorenyl)titanium dichloride, bis(cyclopentadienyl)titanium chlorohydride, bis(cyclopentadienyl)methyltitanium dich
- Transition metal compounds having two conjugated, 5-membered cyclic ligands, in which the two ligands are crosslinked with an alkylene group such as methylenebis(indenyl)titanium dichloride, ethylenebis(indenyl)titanium dichloride, methylenebis(indenyl)titanium chlorohydride, ethylenebis(indenyl)methyltitanium chloride, ethylenebis(indenyl)methoxychlorotitanium, ethylenebis(indenyl)titanium diethoxide, ethylenebis(indenyl)dimethyltitanium, ethylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride, ethylenebis(2-methylindenyl)titanium dichloride, ethylenebis(2,4-dimethylindenyl)titanium dichloride, ethylenebis(2-methyl-4-trimethylsilylindenyl)titan
- Transition metal compounds having two silylene-crosslinked, conjugated, 5-membered cyclic ligands such as dimethylsilylenebis(indenyl)titanium dichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride, dimethylsilylenebis(2-methylindenyl)titanium dichloride, dimethylsilylenebis(2,4-dimethylindenyl)titanium dichloride, dimethylsilylenebis(2,4-dimethylcyclopentadienyl)(31,51-dimethylcyclopentadienyl)titanium dichloride, phenylmethylsilylenebis(indenyl)titanium dichloride, phenylmethylsilylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride, phenylmethylsilylenebis(2,4-dimethylindenyl)titanium
- Transition metal compounds having two conjugated, 5-membered cyclic ligands, in which the two ligands are crosslinked with a germanium-, aluminium-, boron-, phosphorus- or nitrogen-containing hydrocarbon group, such as dimethylgermylenebis(indenyl)titanium dichloride, dimethylgermylene(cyclopentadienyl)(fluorenyl)titanium dichloride, methylalumylenebis (indenyl) titanium dichloride, phenylamylenebis(indenyl)titanium dichloride, phenylphosphylenebis(indenyl)titanium dichloride, ethylborylenebis(indenyl)titanium dichloride, phenylamylenebis(indenyl)titanium dichloride, phenylamylene(cyclopentadienyl)(fluorenyl)titanium dichloride, etc.
- Transition metal compounds having one conjugated, 5-membered cyclic ligand such as pentamethylcyclopentadienyl-bis(phenyl)aminotitanium dichloride, indenyl-bis(phenyl)aminotitanium dichloride, pentamethylcyclopentadienyl-bis(trimethylsilyl)aminotitanium dichloride, pentamethylcyclopentadienylphenoxytitanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)-phenylaminotitanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)-t-butylaminotitanium dichloride, dimethylsilylene(tetrahydroindenyl)decylaminotitanium dichloride, dimethylsilylene(tetrahydroindenyl)-[bis(trimethylsilyl)amino]titanium dichloride,
- Transition metal compounds having two conjugated, 5-membered cyclic ligands in which the ligands are double-crosslinked such as (1,1′-dimethylsilylene)(2,21-isopropylene)bis(cyclopentadienyl)titanium dichloride, (1,1′-dimethylsilylene)(2,2′-dimethylsilylene)-bis(cyclopentadienyl)titanium dichloride, (1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)dimethyltitanium, (1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)dibenzyltitanium, (1,1′-dimethylsilylene)(2,2′-isopropylidene)-bis(cyclopentadienyl)bis(trimethyls
- transition metal compounds of formula (4) As specific examples of the transition metal compounds of formula (4), mentioned are the following compounds.
- transition metal compounds of formula (4) in which the group (C 5 H 5-e R 11 e ) is any of the following formulae (I) to (VII): wherein A represents an element of Group 13, 14, 15 or 16, and plural A's maybe the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or akylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a
- the group (C 5 H 5-e R 11 e ) includes, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,2,3-trimethylcyclopentadienyl group, a 1,3,4-trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, an ethylcyclopentadienyl group, a 1,2-diethylcyclopentadienyl group, a 1,3-diethylcyclopentadienyl group, a 1,2,3-triethylcyclopentadienyl group, a 1,3,4-triethylcyclopentadienyl group, a tetraethy
- transition metal compounds of formula (4) are mentioned below.
- titanium may be replaced with zirconium, and such zirconium compounds are also referred to herein to the same effect.
- cyclopentadienyltitanium trichloride cyclopentadienyltitaniumtrimethyl, cyclopenadienyltitanium trimethoxide, cyclopentadienyltitaniumtribenzyl, methylcyclopentadienyltitanium trichloride, methylcyclopentadienyltitaniumtrimethyl, methylcyclopentadienyltitanium trimethoxide, methylcyclopentadienyltitaniumtribenzyl, dimethylcyclopentadienyltitanium trichloride, dimethylcyclopentadienyltitaniumtrimethyl, dimethylcyclopentadienyltitanium trimethoxide, dimethylcyclopentadienyltitaniumtribenzyl, trimethylcyclopentadienyltitanium trichloride, trimethylcyclopentadienyltit
- transition metal compounds of formula (5) include tetramethyltitanium, tetrabenzyltitanium, tetraethyltitanium, tetraphenyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrephenoxytitanium, tetra(dimethylamino) titanium, tetra(diethylamino) titanium, tetra(diphenylamino)titanium; bis(phenoxy)titanium compounds described in Macromolecules, 1997, 30, 1562-1569, in Journal of Organometallic Chemistry, 514 (1996), 213-217, etc.; diamidotitanium compounds described in Macromolecules, 1996, 29, 5241-5243, in Organometallics, 1997, 16, 1491-1496, etc.; their derivatives to be produced by substituting the titanium element in those compounds with zirconium or hafnium
- M 2 represents a transition metal of Groups B to 10 of the Periodic Table, concretely including iron, cobalt, nickel, palladium, platinum, etc. Of those, preferred are nickel and palladium.
- L 1 and L 2 each represents a coordination-bonding ligand; and X 1 and Y 1 each represent a covalent-bonding or ionic-bonding ligand.
- X 1 and Y 1 include, for example, a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20, preferably from 1 to 10 carbon atoms, an alkoxy group having from 1 to 20, preferably from 1 to 10 carbon atoms, an amino group, a phosphorus-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a diphenylphosphine group, etc.), a silicon-containing hydrocarbon group having from 1 to 20, preferably from 1 to 12 carbon atoms (e.g., a trimethylsilyl group, etc.), and a boron compound residue having a hydrocarbon group with from 1 to 20, preferably from 1 to 12 carbon atoms or having halogens (e.g., B(C 6 H 5 ) 4 , BF 4 ).
- halogen atoms and hydrocarbon groups preferred are halogen atoms and hydrocarbon groups.
- X 1 and Y 1 may be the same or different ones.
- Specific examples of L 1 and L 2 include triphenylphosphine, acetonitrile, benzonitrile, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, 1,1′-bisdiphenylphosphinoferrocene, cyclooctadiene, pyridine, bistrimethylsilylaminobistrimethylsilyliminophosphorane, etc.
- L 1 , L 2 , X 1 and Y 1 may be bonded to each other to form a cyclic structure.
- the compounds of transition metals of Groups 8 to 10 of the Periodic Table preferably have a diimine compound as the ligand, including, for example, complex compounds of a general formula (1-7): wherein R 17 and R 20 each independently represent an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, or an aromatic group having a hydrocarbon group on the ring and having from 7 to 20 carbon atoms in total; R 18 and R 19 each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms, and R 18 and R 19 may be bonded to each other to form a ring; X and Y each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms; and M 2 represents a transition metal of Groups 8 to 10 of the Periodic Table.
- R 17 and R 20 each independently represent an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, or an aromatic group having a hydrocarbon group on the ring and having from 7 to 20 carbon atom
- the aliphatic hydrocarbon group having from 1 to 20 carbon atoms for R and R 20 may be a linear or branched alkyl group having from 1 to 20 carbon atoms or a cycloalkyl group having from 3 to 20 carbon atoms, concretely including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, etc.
- a suitable substituent such as a lower alkyl group or the like may be introduced.
- the aromatic group having a hydrocarbon group on the ring and having from 7 to 20 carbon atoms in total includes, for example, phenyl and naphthyl groups with at least one linear, branched or cyclic C1-10 alkyl group being on the aromatic ring.
- R 17 and R 20 preferred is an aromatic group having a hydrocarbon group on the ring, and especially preferred is a 2,6-diisopropylphenyl group.
- R 17 and R 2 may be the same or different.
- the hydrocarbon group having from 1 to 20 carbon atoms for R 18 and R 19 includes, for example, a linear or branched alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, and an aralkyl group having from 7 to 20 carbon atoms.
- a linear or branched alkyl group having from 1 to 20 carbon atoms and the cycloalkyl group having from 3 to 20 carbon atoms for R 18 and R 19 referred to are those of the C1-20 aliphatic hydrocarbon group mentioned hereinabove for R 17 and R 20 .
- the aryl group having from 6 to 20 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group, etc.; and the aralkyl group having from 7 to 20 carbon atoms includes, for example, a benzyl group, a phenethyl group, etc.
- R 17 and R 18 may be the same or different, and may be bonded to each other to form a ring.
- hydrocarbon group having from 1 to 20 carbon atoms for X and Y, referred to are those of the C1-20 hydrocarbon group mentioned hereinabove for R 18 and R 19 .
- X and Y especially preferred is a methyl group.
- X and Y may be the same or different.
- the transition metal of Groups 8 to 10 of the Periodic Table for M 2 includes, for example, nickel, palladium, platinum, iron, cobalt, rhodium, ruthenium, etc. Preferred are nickel and palladium.
- complex compounds of formula (7) are compounds of the following formulae [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11] and [12].
- transition metal compounds of formula (7) include dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo(1,2-bisdiphenylphosphinoethane) nickel, dibromo(1,3-bisdiphenylphosphinopropane) nickel, dibromo(1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbisdiphenylphosphine nickel, dimethyl(1,2-bisdiphenylphosphinoethane) nickel, methyl(1,2-bisdiphenylphosphinoethano)nickel tetrafluoroborate, (2-diphenylphosphino-1-phenylethyleneoxy)phenylpyridine nickel, dichlorobistriphenylphosphine palladium, dichlorodibenzonitrile palladium, dichlorodiacetonitrile pal
- cationic complexes such as methyl(1,2-bisdiphenylphosphinoethano)nickel tetrafluoroborate, bistriphenylphosphinopalladium bistetrafluoroborate, and bis(2,2′-bipyridino)methyliron tetrafluoroborate etherate.
- R 21 to R 27 each represent an alkyl group having from 1 to 8 carbon atoms, concretely including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, all types of butyl groups, all types of pentyl groups, all types of hexyl group, all types of heptyl groups, and all types of octyl groups.
- R 21 to R 27 may be the same or different; and R 26 and R 27 may be the same or different.
- Y 2 to Y 6 each represent an element of Group 13 of the Periodic Table, concretely including B, Al, Ga, In and Tl. Of these, preferred are B and Al.
- Y 2 to Y 4 may be the same or different; and Y 5 and Y 6 may be the same or different.
- a to d each indicates a number of from 0 to 50, but (a+b) and (c+d) each must be at least 1.
- a to d each preferably falls between 1 and 20, more preferably between 1 and 10, even more preferably between 1 and 5.
- oxygen-containing compound for the catalyst component preferred are alkylaluminoxanes.
- Preferred examples of the compound are methylaluminoxane and isobutylaluminoxane.
- the compound capable of reacting with a transition metal compound to form an ionic complex includes coordination complex compounds that comprise an anion with plural groups bonded to a metal, and a cation, and Lewis acids.
- various coordination complex compounds that comprise an anion with plural groups bonded to a metal, and a cation are preferably used in the invention. ([L 3 -H] g+ ) h ([M 3 X 2 X 3 . . . X n ] (n-m)- ) i (10) ([L 4 ] g+ ) h ([M 4 X 2 X 3 . . .
- L 4 indicates M 5 , R 28 R 29 M 6 or R 30 3C, which will be mentioned hereinafter;
- L 3 represents a Lewis base;
- M 3 and M 4 each represent a metal selected from Group 5 to Group 15 of the Periodic Table;
- M 5 represents a metal selected from Group 1, and Group 8 to Group 12 of the Periodic Table;
- M 6 represents a metal selected from Group 8 to Group 10 of the Periodic Table;
- X 2 to X n each represent a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organometalloid group, or a halogen atom;
- R 28 and R 29 each represent a cyclopentadienyl group, a substituted cyclopent
- M 3 and M 4 include atoms of B, Al, Si, P, As, Sb, etc.; those of M 5 include atoms of Ag, Cu, Na, Li, etc.; and those of M 6 include atoms of Fe, Co, Ni, etc.
- substituted cyclopentadienyl group for R 28 and R 29 include a methylcyclopentadienyl group, a butylcyclopentadienyl group, a pentamethylcyclopentadienyl group, etc.
- the anion with plural groups bonded to a metal includes B(C 6 F 5 ) 4 ⁇ , B(C 6 HF 4 ) 4 ⁇ , B(C 6 H 2 F 3 ) 4 ⁇ , B(C 6 H 3 F 2 ) 4 ⁇ , B(C 6 H 4 F) 4 ⁇ , B[C 6 (CF 3 )F 4 ] 4 ⁇ , B(C 6 H 5 ) 4 ⁇ , PF 6 ⁇ , P(C 6 F 5 ) 6 ⁇ , Al(C 6 HF 4 ) 4 ⁇ , etc.
- the cation includes, for example, CP 2 Fe + , (MeCp) 2 Fe + , (tBuCp) 2 Fe + , (Me 2 CP) 2 Fe + , (Me 3 CP) 2 Fe + , (Me 4 CP) 2 Fe + , (Me 5 CP) 2 Fe + , Ag + , Na + , Li + , etc.
- the other cations include, for example, those from nitrogen-containing compounds, such as pyridinium, 2,4-dinitro-N,N-diethylanilinium, diphenylammonium, p-nitroanilinium, 2,5-dichloroanilinium, p-nitro-N,N-dimethylanilinium, quinolinium, N,N-dimethylanilinium, N,N-diethylanilinium, etc.; those from carbenium compounds such as triphenylcarbenium, tri(4-methylphenyl)carbenium, tri(4-methoxyphenyl)carbenium, etc.; alkylphosphonium ions such as CH 3 PH 3 + , C 2 H 5 PH 3 + , C 3 H 7 PH 3 + , (CH 3 ) 2 PH 2 + , (C 2 H 5 ) 2 PH 2 + , (C 3 H 7 ) 2 PH 2 + , (CH 3 ) 3 PH + ,
- Preferred examples of the compounds of formula (10) include triethylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis(pentafluorophenyl)borate, pyrrolinium tetra(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, methyldiphenylammonium tetraphenylborate, tri(n-butyl)ammonium te
- Preferred examples of the compounds of formula (11) include ferrocenium tetraphenylborate, dimethylferrocenium tetrakis(pentafluorophenyl)borate, ferrocenium tetrakis(pentafluorophenyl)borate, decamethylferrocenium tetrakis(pentafluorophenyl)borate, acetylferrocenium tetrakis(pentafluorophenyl)borate, formylferrocenium tetrakis(pentafluorophenyl)borate, cyanoferrocenium tetrakis (pentafluorophenyl)borate, silver tetraphenylborate, silver tetrakis(pentafluorophenyl)borate, trityl tetraphenylborate, trityl tetrakis (pentafluoropheny
- the Lewis acid includes, for example, B(C 6 F 5 ) 3 , B(C 6 HF 4 ) 3 , B(H 2 F 3 ) 3 , B(C 6 H 3 F 2 ) 3 , B(C 6 H 4 F) 3 , B(C 6 H 5 ) 3 , BF 3 , B[C 6 (CF 3 )F 4 ] 3 , PF 5 , P(C 6 F 5 ) 5 , Al(C 6 HF 4 ) 3 , etc.
- R 1 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R 1 's may be the same or different, and R 1 's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R 2 represents a hydrocarbon group; m is
- X is carbon, Y is oxygen and Z is aluminium;
- at least one of three R 1 's is an aromatic hydrocarbon group having from 6 to 30 carbon atoms;
- three R 1 's are all hydrocarbon groups each having at least one carbon atom;
- three R 1 's are all aromatic hydrocarbon groups each having from 6 to 30 carbon atoms, preferably phenyl groups;
- R 2 is an alkyl group having at least 2 carbon atoms.
- R 1 's are all phenyl groups
- X is carbon
- Y is oxygen
- Z is aluminium
- n 1 is aluminium
- R 2 is an isobutyl group.
- the compounds for the component (C) are not specifically defined for their production method, so far as they have the structure of the formula mentioned above, but preferred are those produced by reacting ⁇ 1> at least one selected from compounds of a general formula, (R 1 ) 3 —C—OR 1 , R 1 —CO—R 1 or R 1 —CO—OR 1 , with ⁇ 2>a compound of a general formula, Z(R 2 )m. (In these formulae, R 1 ,Z or R 2 are same as described above.)
- reaction products of at least one selected from alcohols, ethers, aldehydes, ketones, carboxylic acids and carboxylates with an aluminium compound.
- reaction products of alcohols with an aluminium compound are the following: (1) at least one of three R 1 's for (R 1 ) 3 is an aromatic hydrocarbon group having from 6 to 30 carbon atoms; (2) three R 1 's for (R 1 ) 3 are all hydrocarbon groups each having at least one carbon atom; (3) three R 1 's for (R 1 ) 3 are all aromatic hydrocarbon groups each having from 6 to 30 carbon atoms, preferably phenyl groups; (4) R 2 is an alkyl group having at least 2 carbon atoms. Concretely, more preferred are those where R 1 's are all phenyl groups, and R 2 is an isobutyl group. Most preferred is a reaction product of triphenylmethyl alcohol with triisobutylaluminium.
- the reaction condition for the compound ⁇ 1> and the compound ⁇ 2> is not specifically defined, but is preferably as follows: They are blended in a ratio by mol, compound ⁇ 1>/compound ⁇ 2> falling between 1/0.1 and 1/10, more preferably between 1/0.5 and 1/2, even more preferably between 1/0.8 and 1/1.2.
- the reaction temperature falls between ⁇ 80° C. and 300° C., more preferably between ⁇ 10° C. and 50° C.
- the reaction time falls between 0.1 minutes and 50 hours, more preferably between 0.1 minutes and 3 hours.
- the solvent for the reaction is not also specifically defined, but is preferably the same one as that for copolymerization to be effected in the presence of the catalyst.
- a compound of the following (C1) and a compound of the following (C2) may be directly added to the site of catalyst production or to the site of copolymerization to form the component (C) in situ.
- the catalyst components are the transition metal compound (A), an oxygen-containing compound, and/or a compound capable of reacting with a transition metal to form an ionic complex(B), the compounds (C1) and (C2), and optionally an alkylating agent (D).
- (C1) is least one selected from compounds of a general formula, (R 2 ) 3 —C—OR 1 , R 1 —CO—R 1 or R 1 —CO—OR 1 ; and (C2) is a 9 compound of a general formula, Z(R 2 ) m .
- RL represents a hydrogen atom, a halogen atom, an aliphatic F, hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and R 1 's may be the same or different, and R 1 may be optionally bonded to each other to form a cyclic structure.
- Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R 2 represents a hydrocarbon group.
- (C1) is at least one selected from alcohols, ethers, aldehydes, ketones, carboxylic acids and carboxylates, preferably from alcohols; and (C2) is an aluminium compound.
- at least one of three R 1 's for (R 1 ) 3 is an aromatic hydrocarbon group having from 6 to 30 carbon atoms;
- three R 1 's for (R 1 ) 3 are all hydrocarbon groups each having at least one carbon atom;
- three R 1 's for (R 1 ) 3 are all aromatic hydrocarbon groups each having from 6 to 30 carbon atoms, preferably phenyl groups;
- the catalyst of the invention for production of olefin-styrene copolymers optionally contains an alkylating agent.
- alkylating agents Various types are known and are usable in the invention, including, for example, alkyl group-having aluminium compounds of a general formula (12): R 31 m Al(OR 32 ) n X 3-m-n (12)
- alkyl group-having aluminium compounds preferred are alkyl group-having aluminium compounds; and more preferred are trialkylaluminium compound and dialkylaluminium compounds. Concretely, they include trialkylaluminiums such as trimethylaluminium, triethylaluminium, tri-n-propylaluminium, triisopropylaluminium, tri-n-butylaluminium, triisobutylaluminium, tri-t-butylaluminium, etc.; dialkylaluminium halides such as dimethylaluminium chloride, diethylaluminium chloride, di-n-propylaluminium chloride, diisopropylaluminium chloride, di-n-butylaluminium chloride, diisobutylaluminium chloride, di-t-butylaluminium chloride, etc.; dialkylaluminium alkoxides such as dimethylaluminium methoxide; dimethylalumin
- dialkylmagnesiums such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, etc.
- dialkylzincs such asdimethylzinc, diethylzinc, di-n-propylethylzinc, diisopropylzinc, etc.
- the order of contacting the constituent components with each other is not specifically defined.
- the components may be contacted with each other in the following manner.
- the order of contacting the component (D) with the other components is not specifically defined.
- the component (A) may be contacted with the component (D); or the component (B) may be contacted with the component (D); or the component (C) may be contacted with the component (D).
- the components (A), (B) and (D) are first contacted all together with each other and then with the component (C).
- the molar ratio of the component (A) to the component (B) may fall between 1/1 and 1/10,000, but preferably between 1/10 and 1/1,000, in terms of the molar ratio to the aluminium atom in (B).
- a boron compound is used as a compound capable of reacting with a transition metal compound to form an ionic complex of the component (B).
- the molar ratio of the component (A) to the component (B) may fall between 1/0.5 and 1/10, but preferably between 1/0.8 and 1/5, in terms of the molar ratio to the boron atom in (B).
- the ratio by mol of the component (A) to the component (C2) referred to is a case where an aluminium compound is used as the component (C2).
- the molar ratio of the component (A) to the component (C2) may fall between 1/0.5and 1/1,000, but preferably between 1/1 and 1/100, in terms of the molar ratio to the aluminium atom in (C2).
- the blend ratio of the component (D) the same as in the case ⁇ 1> shall apply also to the case ⁇ 2>.
- the constituent components may be contacted with each other in an inert atmosphere of nitrogen or the like, at a temperature not higher than the temperature at which the catalyst is used for copolymerization. As the case may be, they may be contacted with each other at a temperature falling between ⁇ 30 and 200° C.
- Olefin for the method are not specifically defined, but preferred are a-olefins having from 2 to 20 carbon atoms. Especially preferred are ethylene and propylene.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc.; halogen-substituted ⁇ -olefins such as hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluor
- Styrenes for the method are not specifically defined, but preferred are styrene, alkylstyrenes, and divinylbenzene. Especially preferred are styrene, ⁇ -methylstyrene, p-methylstyrene and divinylbenzene.
- styrene examples include styrene; alkylstyrenes such as p-methylstyrene, p-ethylstyrene, p-prorylstyrene, p-isopropylstyrene, p-buthylstyrene, p-tert-buthlstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-prorylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-buthylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyren
- one or more olefins or styrenes such as those mentioned above may be copolymerized in any desired combination.
- the method for polymerizing olefins and styrenes is not specifically defined and may be any ordinary one including, for example, slurry copolymerization, solution copolymerization, vapor-phase copolymerization, bulk copolymerization, suspension copolymerization, etc.
- the order of contacting the catalyst components with monomers is not also specifically defined.
- One embodiment comprises contacting the catalyst components with each other to prepare a catalyst in advance in the manner mentioned above, followed by applying monomers to the catalyst batch.
- Another comprises putting the catalyst components and monomers into a copolymerization reactor in any desired order.
- the components except the component (C) or except the components (C1) and (C2), or that is, the components (A), (B) and (D) are blended in a reactor, while, on the other hand, monomers are blended with the component (C) or with the components (C1) and (C2) in a different reactor, and the two blends in different reactors are mixed just before the start of copolymerization of the monomers. Having been thus blended, the monomers begin to polymerize in the presence of the catalyst formed in situ.
- a solvent may be used.
- the solvent includes hydrocarbons and halogenohydrocarbons such as benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.
- hydrocarbons and halogenohydrocarbons such as benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.
- benzene toluene
- xylene n-hexane
- n-heptane cyclohexane
- methylene chloride chloroform
- 1,2-dichloroethane chlorobenzene
- the monomers to be polymerized
- the amount of the catalyst to be used for the copolymerization is preferably so controlled that the component (A) may fall generally between 0.1 and 100 ⁇ mols, but preferably between 0.5 and 25 ⁇ mols, in one liter of the solvent, in view of the copolymerization activity and the reactor efficiency.
- the pressure may fall generally between normal pressure and 2000 kg/cm 2 G (196 MPaG).
- the reaction temperature may fall generally between ⁇ 50 and 250° C.
- the type and the amount of the catalyst components to be used and the copolymerization temperature shall be suitably controlled, or hydrogen may be introduced into the copolymerization system.
- the olefin-sterene copolymer by the copolymerization of olefins and styrenes using above mentioned catalyst includes polystyrene, poly(substitutedstyrenes), poly(vinylbenzoate esters) and the mixture of them, or a copolymer comprising them as a main component.
- Poly(substitutedstyrenes) include poly(hydrocarbon substitutedstyrenes) such as poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenylstyrene), poly(vinylstyrene) etc; poly(hologen substitutedstyrenes) such as poly(chlorostyrene), poly(bromostyrene), poly(fluorostyrene) etc; poly(alkoxystyrenes) such as poly(methoxystyrene), poly(ethoxystyrene) etc.
- hydrocarbon substitutedstyrenes such as poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenylstyrene), poly(
- Preferable olefin-sterenic copolymers are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly (p-chlorostyrene),poly (m-chlorostyrene), poly(p-fluorostyrene), a copolymer of styrene and p-tert-buthylstyrene, and a copolymer of styrene and divinylbenzene.
- toluene 180 ml of toluene, 200 ml of styrene, 1.0 ml of a toluene solution of 1.0 M triisobutylaluminium, 3.5 ml of a toluene solution of 1.43 M methylaluminoxane, and 5 ml of the component (C) prepared in the step (1) were put into a 1.6-liter autoclave equipped with a catalyst feeder tube, in that order, and heated up to 50° C. Next, ethylene was introduced into the autoclave to have a pressure of 0.294 MPaG (3 kg/cm 2 G).
- the ethylene-styrene copolymer weighed 47.2 g.
- its weight-average molecular weight was 190,000 in terms of polystyrene, and its molecular weight distribution was 2.4.
- the styrene content of the copolymer was 39 mol %.
- the structure of random copolymer was identified.
- Example 1 The same process as in Example 1 was repeated, except that the component (C) prepared in the step of Example 1 (1) was not added to the copolymerization system in the step of Example 1 (2).
- herein obtained was 30.9 g of ethylene-styrene copolymer.
- its weight-average molecular weight was 200,000 in terms of polystyrene, and its molecular weight distribution was 2.6.
- the styrene content of the copolymer was 37 mol %.
- 13 C-NMR the structure of randomcopolymer was identified.
- the ethylene-styrene copolymer weighed 16.2 g.
- the styrene content of the copolymer was 99 mol %.
- the structure of randomcopolymer was identified.
- Ethylene was continuously introduced into the autoclave so as to have all the time the constant pressure of 3.0 kg/cm 2 G (0.294 MpaG), and copolymerized for 1 hour.
- methanol was added to this to stop the copolymerization.
- a large amount of methanol was added to this, and the polymer formed was separated through filtration, and then dried at 60° C. under reduced pressure for 4 hours.
- the ethylene-styrene copolymer weighed 6.7 g.
- the styrene content of the copolymer was 99 mol %.
- olefin-styrene copolymers can be produced efficiently and inexpensively.
Abstract
Description
- 1. A catalyst for copolymerization of olefins and styrenes, which comprises:
- (A) a transition metal compound,
- (B) an oxygen-containing compound,
- (C) a compound of a general formula (1):
((R1)3—X—Y)n-Z—(R2)m-n (1) - wherein R1 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, a an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R1's may be the same or different, and R1's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R2 represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m-1),
- and optionally,
- (D) an alkylating agent.
- 2. A catalyst for copolymerization of olefins and styrenes, which comprises:
- (A) a transition metal compound,
- (C) a compound of a general formula (1):
((R1)3—X—Y)n-Z—(R2)m-n (1) - wherein R1 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R1's may be the same or different, and R1's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R2 represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m-1),
- and optionally,
- (D) an alkylating agent.
- 3. The catalyst of above 1 or 2 for copolymerization of olefins and styrenes, wherein, in (C), X is carbon, Y is oxygen and Z is aluminium.
- 4. The catalyst of above 1 or 2 for copolymerization of olefins and styrenes, wherein the compound (C) is a reaction product of <1>at least one selected from compounds of a general formula, (R1)3—C—OR3, R4—CO—R5 or R6—CO—OR7, with <2>a compound of a general formula, Z(R2)m. (In these formulae, R1, R3, R4, R5, R6 and R7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and R1, R3, R1, R5, R6 and R7 may be the same or different, and R1,R3, R4, R5, R6 and R7 may be optionally bonded to each other to form a cyclic structure; Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R2 represents a hydrocarbon group.)
- 5. A catalyst for copolymerization of olefins and styrenes, which comprises:
- (A) a transition metal compound,
- (B) an oxygen-containing compound, and/or a compound capable of reacting with a transition metal compound to form an ionic complex,
- (C1) at least one selected from compounds of a general formula, (R1)3—C—OR3, R4—CO—R5 or R6—CO—OR7 (In these formulae, R1,R3, R4, R5, R6 and R7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group, having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and R1,R3, R4, R5, R6 and R7 may be the same or different, and R1,R3, R4, R5, R6 and R7 may be optionally bonded to each other to form a cyclic structure.)
- (C2) a compound of a general formula, Z(R2)m. (In this formula; Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R2 represents a hydrocarbon group.), and optionally,
- (D) an alkylating agent.
- 6. A catalyst for copolymerization of olefins and styrenes, which comprises:
- (A) a transition metal compound,
- (C1) at least one selected from compounds of a general formula, (R1)3—C—OR3, R4—CO—R5 or R6—CO—OR7 (In these formulae, R1,R3, R4, R5, R6 and R7 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, and R1,R3, R4, R5, R6 and R7 may be the same or different, and R1,R3, R4, R5, R6 and R7 may be optionally bonded to each other to form a cyclic structure.
- (C2) a compound of a general formula, Z(R2)m, wherein Z represents a metal element of Groups 2 to 13; m is an integer, indicating the valency of the metal element Z; and R2 represents a hydrocarbon group, and optionally,
- (D) an alkylating agent.
- 7. The catalyst of any of above 1 to 6 for copolymerization of olefins and styrenes, wherein at least one of three R1's is an aromatic hydrocarbon group having from 6 to 30 carbon atoms.
- 8. The catalyst of any of above 1 to 6 for copolymerization of olefins and styrenes, wherein three R1's are all aromatic hydrocarbon groups each having from 6 to 30 carbon atoms.
- 9. The catalyst of any of above 1 to 6 for copolymerization of olefins and styrenes, wherein three R1's are all phenyl groups.
- 10. The catalyst of any of above 1 to 9 for copolymerization of olefins and styrenes, wherein R2 is an alkyl group having at least 2 carbon atoms.
- 11. The catalyst of any of above 4 to 10 for copolymerization of olefins and styrenes, wherein Z is aluminium.
- 12. The catalyst of any of above 1 to 11 for copolymerization of olefins and styrenes, wherein the transition metal compound (A) is represented by any of the following general formulae (2) to (6):
Q1 a(C5H5-a-bR8 b)(C5H5-a-cR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d)Z1M1X1Y1 (3)
(C5H5-eR11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)- in which Q1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H5-a-bR10 b) and (C5H5-a-cR9 c); Q2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C5H5-a-dR10 d) and the group Z1; R8, R9, R10 and R11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; e is an integer of from 0 to 5; M1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M2 represents a transition metal of Groups 8 to 10 of the Periodic Table; L1 and L2 each represent a coordination-bonding ligand; X1, Y1, Z1, W1 and U1 each represent a covalent-bonding or ionic-bonding ligand; and L1, L2, X1, Y1Z1, W1 and U1 may be bonded to each other to form a cyclic structure.
- 13. The catalyst of above 12 for copolymerization of olefins and styrenes, wherein, in the transition metal compound (A) of formula (4), the group (C5H5-eR11 e) is represented by any of the following general formulae (I) to (VII):
- wherein A represents an element of Group 13, 14, 15 or 16, and plural A's may be the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or alkylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
- 14. A method for producing olefin-styrene copolymers, which comprises copolymerizing olefins and styrenes in the presence of the copolymerization catalyst of any of above 1 to 13.
- I. Catalyst for copolymerization of olefins and styrenes:
- 1. Components of catalyst for copolymerization of olefins and styrenes:
Q1 a(C5H5-a-bR9 c) (C5H5-a-cR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d) Z1M1X1Y1 (3)
(C5H5-eR11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)
- wherein Q1 represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C5H5a-bR8 b) and (C5H5a-cR9 c); Q2 represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C5H5-a-dR10 d) and the group Z1; R6, R9, R10 and R11 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure; a represents 0, 1 or 2; b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2; e is an integer of from 0 to 5; M1 represents a transition metal of Groups 4 to 6 of the Periodic Table; M2 represents a transition metal of Groups 4 to 10 of the Periodic Table; L1 and L2 each represent a coordination-bonding ligand; X1, Y1, Z1, W1and U1each represent a covalent-bonding or ionic-bonding ligand; and L1, L2, X1, Y1, Z1, W1 and U1 may be bonded to each other to form a cyclic structure.
wherein A represents an element of Group 13, 14, 15 or 16, and plural A's maybe the same or different; R represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, a carboxyl group, or an alkylsilyl or akylsilylalkyl group having from 3 to 30 carbon atoms, and R's may be the same or different, and may be optionally bonded to each other to form a cyclic structure; a represents 0, 1 or 2; and n and m each represent an integer of at least 1.
wherein R17 and R20 each independently represent an aliphatic hydrocarbon group having from 1 to 20 carbon atoms, or an aromatic group having a hydrocarbon group on the ring and having from 7 to 20 carbon atoms in total; R18 and R19 each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms, and R18 and R19 may be bonded to each other to form a ring; X and Y each independently represent a hydrogen atom, or a hydrocarbon group having from 1 to 20 carbon atoms; and M2 represents a transition metal of Groups 8 to 10 of the Periodic Table.
and/or those of a general formula (9):
([L3-H]g+)h([M3X2X3 . . . Xn](n-m)-)i (10)
([L4]g+)h([M4X2X3 . . . Xn] (n-m)-)i (11)
wherein L4 indicates M5, R28R29M6 or R303C, which will be mentioned hereinafter; L3 represents a Lewis base; M3 and M4 each represent a metal selected from Group 5 to Group 15 of the Periodic Table; M5 represents a metal selected from Group 1, and Group 8 to Group 12 of the Periodic Table; M6 represents a metal selected from Group 8 to Group 10 of the Periodic Table; X2 to Xn each represent a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organometalloid group, or a halogen atom; R28 and R29 each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group; R30 represents an alkyl group; m indicates the valency of M3 or M4, and represents an integer of from 1 to 7; n represents an integer of from 2 to 8; g indicates the ion valency of L3-H or L4, and represents an integer of from 1 to 7; h represents an integer of 1 or more; and i=h×g/(n-m).
((R1)3—X—Y)n-Z—(R2)m-n (1)
wherein R1 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having from 1 to 30 carbon atoms, an aromatic hydrocarbon group having from 6 to 30 carbon atoms, an alkoxy group having from 1 to 30 carbon atoms, an aryloxy group having from 6 to 30 carbon atoms, a thioalkoxy group having from 1 to 30 carbon atoms, a thioaryloxy group having from 6 to 30 carbon atoms, an amino group, an amido group, or a carboxyl group, R1's may be the same or different, and R1 's may be optionally bonded to each other to form a cyclic structure; X represents an element of Group 14; Y represents an element of Group 16; Z represents a metal element of Groups 2 to 13; R2 represents a hydrocarbon group; m is an integer, indicating the valency of the metal element Z; and n is an integer of from 1 to (m-1),
-
- (4) R2 is an alkyl group having at least 2 carbon atoms. More concretely, the most preferred combination is (C1) of triphenylmethyl alcohol and (C2) of triisobutylaluminium.
(D) Alkylating Agent:
- (4) R2 is an alkyl group having at least 2 carbon atoms. More concretely, the most preferred combination is (C1) of triphenylmethyl alcohol and (C2) of triisobutylaluminium.
R31 mAl(OR32)nX3-m-n (12)
-
- wherein R3′ and R32 each represent an alkyl group having from 1 to 0, preferably from 1 to 4 carbon atoms; X represents a hydrogen atom or a halogen atom; 0<m<3, but preferably m is 2 or 3, most preferably 3; 0≦n<3, but preferably n is 0 or 1;
alkyl group-having magnesium compounds of a general formula (13):
R31 2Mg (13) - wherein R31 has the same meaning as above; and alkyl group-having zinc compounds of a general formula (14):
R31 2Zn (14) - wherein R28 has the same meaning as above.
- wherein R3′ and R32 each represent an alkyl group having from 1 to 0, preferably from 1 to 4 carbon atoms; X represents a hydrogen atom or a halogen atom; 0<m<3, but preferably m is 2 or 3, most preferably 3; 0≦n<3, but preferably n is 0 or 1;
-
- (ii) For producing the catalyst comprising the component (A), the component (B), the component (C1) and the component (C2), the order of contacting these components with each other is not also specifically defined, like in the case (i). Preferably, however, the component (C1) and the component (C2) are first contacted with each other prior to being contacted with the other components. The same as in the case (i) shall apply also to the case (ii) of producing the catalyst containing the optional component (D).
- (iii) In the case of which does not use the component (B), the order of contacting these components with each other is the same as mentioned above.
(2) Blend ratio of Constituent Components: - (i) In the case of using the component (B):
-
- (ii) In the Both Cases of Using the Component (B) and not Using the Component (B):
<1>Regarding the ratio by mol of the component (A) to the component (C), referred to is a case where an aluminium compound is used as the component (C). In that case, the molar ratio of the component (A) to the component (C) may fall between 1/0.5 and 1/1,000, but more preferably between 1/1 and 1/100, in terms of the molar ratio to the aluminium atom in (C). Regarding the ratio by mol of the component (A) to the component (D), referred to is a case where an aluminium compound is used as the component (D). In that case, the molar ratio of the component (A) to the component (D) may fall between 1/0.5 and 1/1,000, but preferably between 1/1 and 1/100, in terms of the molar ratio to the aluminium atom in (D).
<2>Where the catalyst contains a combination of the component (C1) and the component (C2), but not the component (C), the molar ratio of (C1) to (C2) may fall between 1/0.1 and 1/10, precisely between 1/0.5 and 1/2, but more preferably between 1/0.8 and 1/1.2.
- (ii) In the Both Cases of Using the Component (B) and not Using the Component (B):
Claims (26)
Q1 a(C5H5-a-bR8 b)(C5H5-a-cR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d) Z1M1X1Y1 (3)
(C5H5,R11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)
((R1)3—X—Y)n-Z—(R2)m-n (1)
R31 mAl(OR32)nX3−m−n (12)
R31 2Mg (13)
R31 2Zn (14)
((R1)3—X—Y)n-Z—(R2)m-n (1)
Q1 a(C5H5-a-bR8 b) (C5H5-a-dR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d) Z1M1X1Y1 (3)
(C5H5-eR11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)
Q1 a(C5H5-a-bR8 b) (C5H5-a-cR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d) Z1M1X1Y1 (3)
(C5H5-eR11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)
Q1 a(C5H5-a-bR8 b)(C5H5-a-cR9 c)M1X1Y1 (2)
Q2 a(C5H5-a-dR10 d) Z1M1X1Y1 (3)
(C5H5-a-eR11 e) M1X1Y1W1 (4)
M1X1Y1W1U1 (5)
L1L2M2X1Y1 (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11050668A JP2000248015A (en) | 1999-02-26 | 1999-02-26 | Catalyst for copolymerizing olefin compound with styrene compound and production of olefin-styrene based copolymer |
PCT/JP2000/001101 WO2000050469A1 (en) | 1999-02-26 | 2000-02-25 | Catalyst for olefin/styrene copolymerization and process for producing olefin/styrene copolymer |
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US6838409B1 true US6838409B1 (en) | 2005-01-04 |
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US09/914,254 Expired - Fee Related US6838409B1 (en) | 1999-02-26 | 2000-02-25 | Catalyst for olefin/styrene copolymerization, and process for producing olefin/styrene copolymer |
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US (1) | US6838409B1 (en) |
EP (1) | EP1167394A4 (en) |
JP (1) | JP2000248015A (en) |
KR (1) | KR20010102335A (en) |
CA (1) | CA2356635A1 (en) |
TW (1) | TWI273108B (en) |
WO (1) | WO2000050469A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050197471A1 (en) * | 1998-09-09 | 2005-09-08 | Sumitomo Chemical Company Limited | Modified aluminum oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocarbon polymer |
US20110172366A1 (en) * | 2007-06-13 | 2011-07-14 | Idemitsu Kosan Co., Ltd. | Olefin/aromatic vinyl copolymer, process for production thereof, resin compositions containing the copolymer, and stretched products of the copolymer |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6495484B1 (en) * | 2000-08-28 | 2002-12-17 | Univation Technologies, Llc | Catalyst system and its use in a polymerization process |
EP1449853B1 (en) * | 2001-10-19 | 2015-06-03 | Asahi Kasei Chemicals Corporation | Process for polymerization of olefins |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4990580A (en) * | 1987-01-22 | 1991-02-05 | Idemitsu Kosan Company Limited | Process for production of styrene polymers |
EP0417313A1 (en) | 1989-03-20 | 1991-03-20 | Idemitsu Kosan Company Limited | Styrenic copolymer and production thereof |
EP0707013A1 (en) | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Catalyst for producing styrene polymer and process for producing styrene polymer using the same |
JPH09165410A (en) | 1995-11-14 | 1997-06-24 | Elf Atochem Sa | Polymerizing method for olefin |
JPH09176220A (en) | 1995-12-27 | 1997-07-08 | Sumitomo Chem Co Ltd | Production of olefin polymer |
JPH09255711A (en) | 1996-03-27 | 1997-09-30 | Mitsui Petrochem Ind Ltd | Olefin polymerization catalyst and process for polymerizing olefin |
JPH09278817A (en) | 1996-04-17 | 1997-10-28 | Idemitsu Kosan Co Ltd | Olefin polymerization catalyst and production of olefinic polymer therewith |
WO1998001485A1 (en) * | 1996-07-05 | 1998-01-15 | Bayer Aktiengesellschaft | Method for producing high melting-point polyolefins |
JPH10168112A (en) | 1996-12-16 | 1998-06-23 | Mitsui Chem Inc | Catalyst for copolymerization of alpha-olefin and aromatic vinyl compound, production of copolymer of alpha-olefin and aromatic vinyl compound, and new transition metal compound |
US5786432A (en) * | 1992-06-27 | 1998-07-28 | Targor Gmbh | Metallocenes containing aryl-substituted indenyl derivatives as ligands, process for their preparation, and their use as catalysts |
US5854165A (en) | 1993-09-30 | 1998-12-29 | Idemitsu Kosan Co., Ltd. | Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer by use of catalyst |
EP0911346A2 (en) | 1997-10-24 | 1999-04-28 | Idemitsu Petrochemical Co., Ltd. | Ethylene copolymer and aromatic vinyl graft copolymer and method for producing the same |
US6107232A (en) * | 1992-12-18 | 2000-08-22 | Idemitsu Kosan Co., Ltd. | Polymerization catalyst and process for preparing polymer by use of same |
US6255244B1 (en) * | 1998-09-14 | 2001-07-03 | Idemitsu Petrochemical Co., Ltd. | Polymerization catalysts for olefinic and styrenic monomer and polymer production method |
US6271313B1 (en) * | 1998-12-21 | 2001-08-07 | The Goodyear Tire & Rubber Company | Styrene-butadiene block copolymer |
US6339135B1 (en) | 1995-03-30 | 2002-01-15 | Idemitsu Kosan Co., Ltd. | Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988008432A1 (en) * | 1987-04-20 | 1988-11-03 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for polymerizing olefin |
US4978730A (en) * | 1987-12-24 | 1990-12-18 | Idemitsu Kosan Company Limited | Process for producing styrene-based polymers and catalyst for use therein |
KR0139089B1 (en) * | 1994-12-08 | 1998-05-01 | 김은영 | The catalyst system for polymerization of olefins |
-
1999
- 1999-02-26 JP JP11050668A patent/JP2000248015A/en active Pending
-
2000
- 2000-02-22 TW TW089103018A patent/TWI273108B/en not_active IP Right Cessation
- 2000-02-25 WO PCT/JP2000/001101 patent/WO2000050469A1/en active Application Filing
- 2000-02-25 CA CA002356635A patent/CA2356635A1/en not_active Abandoned
- 2000-02-25 US US09/914,254 patent/US6838409B1/en not_active Expired - Fee Related
- 2000-02-25 EP EP00905347A patent/EP1167394A4/en not_active Withdrawn
- 2000-02-25 KR KR1020017010714A patent/KR20010102335A/en not_active Application Discontinuation
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4990580A (en) * | 1987-01-22 | 1991-02-05 | Idemitsu Kosan Company Limited | Process for production of styrene polymers |
EP0417313A1 (en) | 1989-03-20 | 1991-03-20 | Idemitsu Kosan Company Limited | Styrenic copolymer and production thereof |
US6242544B1 (en) * | 1992-06-27 | 2001-06-05 | Targor Gmbh | Metallocenes containing aryl-substituted indenyl ligands and their use as catalysts |
US5786432A (en) * | 1992-06-27 | 1998-07-28 | Targor Gmbh | Metallocenes containing aryl-substituted indenyl derivatives as ligands, process for their preparation, and their use as catalysts |
US6107232A (en) * | 1992-12-18 | 2000-08-22 | Idemitsu Kosan Co., Ltd. | Polymerization catalyst and process for preparing polymer by use of same |
EP0707013A1 (en) | 1993-07-02 | 1996-04-17 | Idemitsu Kosan Company Limited | Catalyst for producing styrene polymer and process for producing styrene polymer using the same |
US5854165A (en) | 1993-09-30 | 1998-12-29 | Idemitsu Kosan Co., Ltd. | Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer by use of catalyst |
US6171994B1 (en) | 1993-09-30 | 2001-01-09 | Idemitsu Kosan Co., Ltd. | Multiple crosslinking type transition metal compound used for olefin polymerization process |
US6339135B1 (en) | 1995-03-30 | 2002-01-15 | Idemitsu Kosan Co., Ltd. | Transition metal compound, catalyst for olefin polymerization, process for preparing olefin polymer |
JPH09165410A (en) | 1995-11-14 | 1997-06-24 | Elf Atochem Sa | Polymerizing method for olefin |
JPH09176220A (en) | 1995-12-27 | 1997-07-08 | Sumitomo Chem Co Ltd | Production of olefin polymer |
JPH09255711A (en) | 1996-03-27 | 1997-09-30 | Mitsui Petrochem Ind Ltd | Olefin polymerization catalyst and process for polymerizing olefin |
JPH09278817A (en) | 1996-04-17 | 1997-10-28 | Idemitsu Kosan Co Ltd | Olefin polymerization catalyst and production of olefinic polymer therewith |
WO1998001485A1 (en) * | 1996-07-05 | 1998-01-15 | Bayer Aktiengesellschaft | Method for producing high melting-point polyolefins |
US6191241B1 (en) * | 1996-07-05 | 2001-02-20 | Bayer Aktiengesellschaft | Method for producing high melting-point polyolefins |
JPH10168112A (en) | 1996-12-16 | 1998-06-23 | Mitsui Chem Inc | Catalyst for copolymerization of alpha-olefin and aromatic vinyl compound, production of copolymer of alpha-olefin and aromatic vinyl compound, and new transition metal compound |
EP0911346A2 (en) | 1997-10-24 | 1999-04-28 | Idemitsu Petrochemical Co., Ltd. | Ethylene copolymer and aromatic vinyl graft copolymer and method for producing the same |
US6255244B1 (en) * | 1998-09-14 | 2001-07-03 | Idemitsu Petrochemical Co., Ltd. | Polymerization catalysts for olefinic and styrenic monomer and polymer production method |
US6271313B1 (en) * | 1998-12-21 | 2001-08-07 | The Goodyear Tire & Rubber Company | Styrene-butadiene block copolymer |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050197471A1 (en) * | 1998-09-09 | 2005-09-08 | Sumitomo Chemical Company Limited | Modified aluminum oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocarbon polymer |
US7211537B2 (en) * | 1998-09-09 | 2007-05-01 | Sumitomo Chemical Company Limited | Modified aluminum oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocarbon polymer |
US20110172366A1 (en) * | 2007-06-13 | 2011-07-14 | Idemitsu Kosan Co., Ltd. | Olefin/aromatic vinyl copolymer, process for production thereof, resin compositions containing the copolymer, and stretched products of the copolymer |
US8461270B2 (en) | 2007-06-13 | 2013-06-11 | Idemitsu Kosan Co., Ltd. | Olefin/aromatic vinyl copolymer, process for production thereof, resin compositions containing the copolymer, and stretched products of the copolymer |
Also Published As
Publication number | Publication date |
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TWI273108B (en) | 2007-02-11 |
CA2356635A1 (en) | 2000-08-31 |
EP1167394A4 (en) | 2005-07-13 |
EP1167394A1 (en) | 2002-01-02 |
JP2000248015A (en) | 2000-09-12 |
KR20010102335A (en) | 2001-11-15 |
WO2000050469A1 (en) | 2000-08-31 |
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